Coating composition



3,455,716 COATING COMPOSITION Lewis D. Loring, Bolton, and Henry J.Voss, Homewood, lll., assignors to Sinclair Research, Inc., New York,N.Y., a corporation of Delaware No Drawing. Continuation-impart ofapplication Ser. No. 229,218, Oct. 8, 1962. This application Apr. 6,1964, Ser. No. 357,764

Int. Cl. C23f 15/ C091: 3/00; B605 5/00 US. Cl. 106-268 9 ClaimsABSTRACT OF THE DISCLOSURE A coating composition, useful for protectingsurfaces from deterioration caused by corrosion, comprising about 25 to75% of a mineral oil base consisting essentially of a petroleum resinhaving an SUS viscosity at 210 F. of about 500 to 20,000 and sufiicientmineral lubricating oil to provide said mineral oil base with aviscosity of about 200 SUS at 100 F. to 1,000 SUS at 210 F., about 10 to20% of a water-insoluble alkaline metal soap of a fatty acid having from12 to 22 carbon atoms; about 1 to 15% of a lead soap of oxidizedpetroleum wax, and sufficient hydrocarbon solvent to provide acomposition having an ASTM work penetration at 77 F. of about 250 to350; wherein a combination of a polybutadiene oil and a heavy metalnaphthenate may be added in an amount suflicient to increase thehardening rate of the coating.

This application is a continuation-in-part of application Ser. No.229,218, filed Oct. 8, 1962, and now abandoned, which in turn is acontinuation-impart of application Ser. No. 212,451, filed July 25,1962, and now abandoned.

This invention relates to a novel composition useful for coatingsurfaces to protect them from deterioration such as caused by corrosion.In a specific application, the composition is employed to undercoatautomobile and other vehicle bodies to guard against corrosion.

Corrosion is the ever present enemy of motor vehicles. While greatprogress has been made in developing protective finishes forautomobiles, the nature and location of corrosion, when it does occur,indicates that there is opportunity for even further improvement. Themost serious corrosion proceeds from underneath or inside the exteriorsurfaces of the car. With the adoption of the unit-frame construction bynearly every car manufacturer the problem of corrosion to the underbodyis being reappraised since corrosion of this unit-frame would cause aweakening of the underbody and would literally speed up a car in fallingapart. The reason is that these sur faces receive less attention fromthe user and are kept wet longer by splash and clinging mud which mayact as a reservoir and medium of concentration for corrosive substances.Also, the underbodies usually do not receive the supplementaryprotective effect of waxes commonly applied by the owner to the otherexterior surfaces.

During recent years there has developed the practice of applying heavy,fiber reinforced asphaltic coatings to car underbodies for the combinedpurposes of corrosion protection and sound deadening. These materialshave not as such been capable of giving the underbody of the car theprotection desired. Due to the many and varied conditions to which anautomobile undercoating is subjected, the coating must withstandtemperature changes such that in cold weather it should be flexible andnot tend to unduly crack and chip and at high temperatures it should benon-flowing and non-tacky. Also, the coating must be able to withstandchemical attack such as from the corrosive effect of the various saltcombinations used 3,455,716 Patented July 15, 1969 for road treatmentduring both summer and winter months.

The present invention is directed towards a coating composition whichcan be applied to surfaces using available equipment; will adhere tometal surfaces and penetrate moderate dirt or moisture accumulation;will harden in a reasonable time but remain plastic or flexible; willprevent rusting or corrosion; will have good resistance to waterwashing; will heal over if the film is ruptured; will not softenexcessively at maximum ambient temperatures nor crack or peel atlowtemperatures; will not have undesirable immediate or residual odor; andwill have acceptable toxicity and flammability limits.

The composition of the present invention is of grease consistency andhas a heavy mineral oil resin containing base, a thickening componentcomprising an essentially water-insoluble alkaline metal soap of a fattyacid, a lead salt of an oxidized wax, a light hydrocarbon solvent, forinstance, boiling in the naphtha to kerosene range and, when desired, ananti-oxidant or other additive agents.

In another embodiment of the present invention, it has been found thatinclusion in the coating composition of small amounts of a combinationof polybutadiene oil and a heavy metal naphthenate substantiallyincreases the rate of surface hardening of the applied coating, in mostcases to two or three times the drying rate ordinarily observed, withoutunduly deleteriously affecting the aforementioned advantages provided bythe composition.

The heavy mineral oil base is about 25 to 70% of the composition andconsists essentially of a petroleum resin with or without a minerallubricating oil. The mineral oil base as such usually has a viscosity inthe range of about 200 SUS at F. to 1000 SUS at 210 F., preferably about400 SUS at 100 F. to 400 SUS at 210 F. regardless of whether it iscomposed of petroleum resin or a mixture of the resin and lubricatingoil. This viscosity is that exhibited by the resin per se or thecombined resin and lubricating oil, if any of the latter be present,even though these components may not be mixed in the absence of otheragents during the actual manufacturing of the composition.

The petroleum resin fractions useful in the present composition give ahardening of the coating composition Without producing brittleness uponapplication to a surface and drying or solvent evaporation, and theresin may be either paraffinic, mixed or aromatic based. The resinsusually have a viscosity of about 500 to 5,000; or even to 20,000preferably about 3,000 to 3,600, SUS at 210 F. The amount of petroleumresin in the composition will generally Ibe in the range of about 5 to70 weight percent. The resin will often not exceed about 20% of thefinal composition and is preferably about 10 to 15% and commensuratewith the viscosity of the overall mineral oil base as previously stated.The resin fraction can be derived from a heavy paraffinic baselubricating oil stock, for instance, a residual oil such as cylinder orbright stock from a paratfinic base crude, or it may be derived fromheavy petroleum distillates and lubricating oil stocks obtained fromnaphthenic or asphaltic base crudes and mixed, e.g. Mid-Continent, basecrudes.

The parafiinic type resin fraction may be the residual materialremaining after conventional solvent extraction of a heavy paraffinicbase lubricating oil stock. For example, to obtain the resin a heavyresidual lubricating oil fraction of a parafiinic base crude can becontacted with a solvent, such as propane, to precipitate the insolubleconstituents of the lubricating oil fraction. This precipitate orextracted residue is subsequently recovered as petroleum resin. Othersolvents, for instance lower alkanes such as ethane or butane, may beused to produce the petroleum resin. These paraflinic petroleum resinsare characterized by their tackiness and high viscosity index, generallyabove v about 90.

Aromatic petroleum resins are high viscosity, highly aromatic materials,for instance remaining after appropriate treatment of heavy petroleumresidues or distillates and lubricating oil stocks obtained fromnaphthenic or asphaltic based crudes or mixed base crudes. The aromaticfractions contain the aromatic constituents of the crude oil with aminimum of paraffinic, naphthenic and asphaltic materials. The aromaticfractions can be derived by the solvent, e.g. phenol, furfural,nitrobenzene and so forth, extraction of heavy bright stocks having aviscosity of more than about 100 Saybolt Universal seconds at 210 F.; bypropane or butane fractionation of the lubricating 'oil extractsobtained from conventional solvent treating of bright stocks lubricatingoils; by vacuum distillation of the lubricating oil extracts obtainedfrom solvent treating lubricating oils; or by chromatographic separationof heavy petroleum distillates and residuals using alumina, clay orsimilar earths as the adsorbent. The aromatic fractions can also beobtained using the process described in US. Patent 2,727,847 in which adeasphalted residual stock is treated with a selective solvent which hasa high selectivity for aromatic components to separate a raw resinousfraction and in which such raw resinous fraction is fractionated at atemperature of about 100 F. to 200 F. with liquid propane, followingwhich there are recovered a high viscosity aromatic resin from thepropane insoluble phase and a deresined extract oil from the propanesoluble phase. The aromatic resin fractions are often characterized byan API gravity below about 15.0 and a V.I. below about 25.

Suitable lubricating oils for our composition generally have a viscosityof about 30 to 2,000 SUS at 100 F., preferably about 75 to 750 SUS at100 F. These mineral lubricating oils may be derived from any petroleumcrude source, whether paraffinic, mixed or naphthenic in type, and maybe refined by any of the refining techniques of the petroleum industry.The amount of lubricating oil present in the final composition isusually in the range of about to 50, preferably about 20 to 40 percentby weight, and sufiicient to obtain the desired viscosity with the resinas noted above.

Our composition is of grease consistency due primarily to the presenceof an essentially water-insoluble alkaline metal soap and the properamounts of the other components. In general, this soap will compriseabout to of the final formulation, and preferably is about 12 to 16%.The overall composition usually has a penetration at 77 F. (ASTM worked)of about 250 to 350, preferably about 290-340" F.

The soap-forming fatty components contemplated in this invention are thesaturated and unsaturated, naturallyoccurring and syntheticgrease-making carboxylic aliphatic fatty acids and their esters, such asthe naturally-occurring or processed fats and oils which are inglyceride form, that are commonly known in the art and contain about 7to 30 carbon atoms in the carboxylic acid group. The preferred fattyacids are the higher fatty acids that have from about 12 to 30 carbonatoms, especially those fatty or alkanoic acids that have from about 12to 22 carbon atoms per molecule. The fatty acids normally used in themanufacture of conventional greases, particularly the saturated acids,are preferred. Suitable fatty acids include lauric, myristic, palmitic,stearic, the various hydroxy stearic acids, oleic, arachidic, behenicand the like. Naturally-occurring fatty acids such as fish oil acids,tallow acids, which contain chiefly oleic, stearic and palmitic acids,coconut oil acids, castor oil, etc., may also be utilized directly orafter hydrogenation to decrease any undesirably high degree ofunsaturation. Mixtures of these high molecular weight fatty acids, e.g.,hydrogenated fish oil acids with oleic acid. are also operable, as arefractions obtained by distillation, extraction or crystallization. Thethickening component may also be formed as a saltsoap complex containinga portion of low molecular weight carboxylic acid, e.g. acetic acid,salt as known in the art.

The alkaline, i.e. the alkali and alkaline earth, metal constituent ofthe fatty component reacts with the carboxylic acid source material toform the metal soap. Ordinarily the metal hydroxide or other inorganiccompound is used when making the soap by reaction with the acidcomponent. The alkaline earth metal hydroxides or carbonates such asthose of calcium, barium and strontium are useful as are the alkalimetal hydroxides such as lithium hydroxide. Calcium hydroxide orhydrated lime is especially preferred, although lithium also gives auseful water-insoluble soap when combined with l2-hydroxy stearic acid.

In preparing the thickening or bodying component of the presentinvention, the soap may be preformed but preferably is made in all or aportion of the mineral oil base. As an example, about 20 to weightpercent of the mineral lubricating oil of that in the final compositionmay be used as the soap-making medium. Thus, the grease composition canbe made by mixing together the desired amount of lubricating oil, lowviscosity resin or a mixture of lubricating oil and resin, with themetal base and the high molecular weight carboxylic acid and allowingthese ingredients to react. The resulting grease can be dehydrated tothe desired extent. In one procedure, a calcium tallow soap grease canbe dehydrated to leave a small amount of stabilizing water or suchgrease can be essentially dehydrated and the small amount of waterre-added. When making anhydrous grease intermediates, external heatingcan be applied within the range of about 220500 F. until the watercontent is generally below about 1 weight percent and preferably belowabout 0.5 weight percent. When the soap is formed from a hydroxy fattymaterial, such as 12-hydroxy stearic acid, the heating may be applieduntil the water present in the grease does not exceed about 0.3 weightpercent, preferably the water is about 0.01 to 0.3 weight percent, seeUS. Patent No. 2,915,467. The exact temperature range which may be usedvaries from one process to another depending upon different proceduralsteps as fully understood by those skilled in the art. When the maximumtemperature is reached, heating may be discontinued and the grease batchcooled to about 250 F. Any of the conventional anti-oxidant additives,such as phenyl alpha naphthylamine, diphenylamines, alkylated amines,etc., may be added at this time, generally in amounts of about 0.1 to2.0 weight percent and the grease is further cooled to below about 200F. The resulting grease may then be homogenized by any of the knownsuitable means, such as for example, a Charlotte colloid mill.

The composition of this invention also includes a lead soap of anoxidized petroleum wax which soap exhibits excellent corrosioninhibiting characteristics and bestows surface hardening properties tothe coating composition when it is present in the range of about 1 to15, preferably about 3 to 8 weight percent, based on the finalcomposition. The metal component forms a soap or salt with therelatively high molecular weight aliphatic carboxylic acids, esters,lactones, etc. derived from a petroleum wax by controlled partialoxidation. The mixed oxygenated hydrocarbons derived from suchcontrolled oxidation consist fundamentally of mixtures of carboxylicacids and their esters ranging from C to C often averaging about Theoxidation process can be carried out in the known manner and generallycomprises blowing air through the wax at elevated temperature, such as atemperature above about 250 F. The reaction is preferably carried out attemperatures in the range of about 270 to 350 F. and at atmospheric ormoderately elevated pressures such as pressures up to about 200 p.s.i.g,employing air rates of about 15-35 standard cubic feet of air per hourper pound of charge. A catalyst such as potassium permanganate orpotassium stearate may be present if desired.

The petroleum oxidate may be extracted with a hydrocar-bon solvent suchas benzene or a petroleum distillate fraction boiling in the range ofabout 100 to 300 F., and preferably a paraffinic hydrocarbon containing5 to 7 carbon atoms. The solvent extraction may be carried out atordinary temperatures or a slightly elevated temperature, employingvarious proportions, of oxidate and solvent usually in the range ofabout 1:1 to 1:4 of oxidate to solvent.

The conversion of the separated saponifiable material into the lead soapmay be carried out by any convenient method, as for example bydistilling off the solvent and treating the saponifiable material with,for instance, lead oxide. Since the conversion to the lead soaps maytake place rather slowly, the saponification reaction may be carried outmore conveniently by first saponifying with an alkali metal hydroxideand then converting the alkali metal soap to the lead soap by acidifyingan aqueous solution of the soap with an inorganic acid and treating therecovered organic acids with lead oxide. Unsaponifiable matter may beremoved if desired by extraction of the soap with a hydrocarbon solventsuch as naphtha or benzene. The hydrocarbon solvent containing thedissolved oxidate may be extracted with an equeous solution containingsufficient alkali metal hydroxide to saponify all of the saponifiablematerial, and the aqueous solution of alkali metal soap obtained maythen be separated from the hydrocarbon solvent which contains theunsaponifiable material. The metal soap usually contains about 3 to 15,preferably about 5 to weight percent of lead based on the weight ofsoap.

The light hydrocarbon solvents suitable for use in the present inventioninclude solvents boiling in the naphtha to kerosene range whichevaporate upon application of the coating composition to the surface tobe protected. Suitable solvents are the essentially odorless petroleumsolvents such as an alkylate of isobutane and propylene. The solvent mayhave a gravity of about 52-56; flash (TCC) of at least 120 F.; Sayboltcolor of at least a minimum of +25 and good odor characteristics. Atypical solvent useful in the present composition has an ASTMdistillation as follows:

The solvent is generally present in the composition in amounts fromabout to 50, preferably about 25 to 40, weight percent and in any eventprovides a composition of grease consistency advantageously having apenetration of about 250 to 350 as set forth above.

As previously mentioned, a combination of polybutadiene oil and a heavymetal naphthenate can be advantageously added to the composition tosignificantly increase the hardening rate of the film coating. Thepolybutadiene oils of the invention are polymers of butadiene which cancontain up to about 40%, preferably up to about 25%, of styrene or othercomonomer. They are mineral oil-miscible, viscous oils having akinematic viscosity at 30 C. of about 100 to 2000 poises, preferablyabout 200 to 1200 poises. The polybutadiene oils are added in amounts ofabout 0.1 to 2%, preferably about 0.4 to 1.8%, by weight of thecomposition. Although the polybutadiene oil is capable by itself ofreducing the hardening rate of the coating film, it was found that theuse of very small amounts of a naphthenate of a heavy metal of to 82atomic number, preferably manganese, cobalt or lead, usually on theorder of about .003 to 06%, preferably about 0.004 to 0.02% by weightheavy metal naphthenate based on the total composition in combinationwith the polybutadiene oil affects the drying activity of thepolybutadiene oil so that the drying time to obtain a hard surfacecoating is reduced significantly, for instance in the case of cobaltnaphthenate, to approximately half or less of the drying time obtainablewith optiumum concentrations of the polybutadiene oils alone, yet theother properties of the composition remain satisfactory, e.g. theapplied composition is not brittle. Larger concentrations of either thepolybutadiene oil or cobalt naphthenate can be employed if desired butlittle if any further improvement has been found. Examples of suitableheavy metal naphthenates are naphthenates of lead, iron, nickel,maganese, tin, cadmium, chromium, zinc, copper, vanadium and the like.The preferred heavy metal naphthenate is cobalt naphthenate.

The polybutadiene oils can be produced by any of the Well-knownpolymerization processes in the art such as sodium catalyzedpolymerization, BF -etherate catalyzed polymerization, emulsionpolymerization as well as bulk polymerization in the presence of adiluent and an or ganic peroxide catalyst. The polybutadiene oils can beadded per se, that is, without dilution but it is preferably premixedwith an equal amount of the light hydrocarbon solvent component of thecoating composition in order to facilitate handling and dispersion ofthe product. Incorporation of the polybutadiene oil is preferablyconducted after blending the other ingredients of the coat- 1ngcomposition.

The addition of the heavy metal naphthenate can be before orsimultaneously with the polybutadiene oils but preferably follows thepolybutadiene oil addition. The heavy metal naphthenate can be added perse but is preferably added as a concentrate in a light hydrocarbondistillate such as kerosene.

A typical example of the composition of the present invention showingexcellent properties for undercoating automobiles is prepared asfollows:

EXAMPLE I A. Preparation of calcium soap.A calcium soap grease wasformed in a steam-jacketed kettle by adding the fatty acid to the kettleand melting at 180 F. To a portion of the starting mineral oil was addeda stoichiometric quantity of a hydrated lime. This mixture plus theremainder of starting oil (1 part per part fatty acid) was added to thekettle. The mixture was heated to 220 F. until it was essentiallydehydrated and then a small amount of flake caustic dissolved in anequal amount of water was included. 12% of water was added as was thecool finishing mineral oil (balance of oil). Anti-oxidants OADA andPlexol B were incorporated and the grease was allowed to cool to roomtemperature. The ingredients employed included:

Component: Weight precent Tallow fatty acids 26.12 Hydrated lime 3.76Flake caustic 0.21 Refined Coastal oil, SUS at 100 F 69.91 Plexol B(2,6-di-(dimethylaminomethyl)-4- octylphenol 0.12 OADA (mixture ofoctylated and styrenated diphenylamines) 0.12

To the above calcium soap grease is added a paraflinic petroleum resinderived from a Pennsylvania base crude. The petroleum resin is heated to190 F. and solwly added to the grease in the kettle. If the petroleumresin and the total mineral oil of the calcium soap grease were mixedthe resultant belend would have had a viscosity of about 500 SUS at 100F. or about 60 to 63 SUS at 210 F. The petroleum resin is characterizedby a viscosity of about 3200 SUS at 210 F. and a viscosity index of 100.Stirring is continued in the kettle until the resin is thoroughlyincorporated. Alox 707, an oxidized wax comprising a mixture of organicacids, lactones, esters, etc.

in which the acids have been converted to lead soaps and characterizedby the following:

Appearance Dark solid Melting point F. (min.) 185 Flash (O.C.) F. (min.)410 Fire (O.C.) F. (min.) 520 Lead content weight percent 7-9 Acid No.-10 Sp. gr. at 158 F 1.05-1.10

Weight percent Calcium grease 53.0

Mineral oil 37.40 Calcium soap of tallow acids 14.80 Water 0.56

Anti-oxidants 0.24

Petroleum resin 13.0

Alox 707 4.0

Petroleum solvent 30.0

The coating composition possessed the following characteristics:

Unworked penetration 302 Worked penetration 320 Dropping point F 202 Thecalcium soap and water of this composition may be replaced by a like orlesser amount of lithium 12-hydroxy stearate to obtain anothercomposition of this invention.

Salt fog and humidity cabinet tests were run on the above calciumsoap-containing composition. These results are reported below:

MIL-L-21260, humidity cabinet, no rust 21 days MIL-L-3150, salt fog, norust 72 hours Also this composition passed the ASTM D1743-60T rust test.

Steel panels sprayed with the above calcium soap-containing coatingcomposition which have been exposed to the atmosphere for over 2 monthsshowed no loss of coating and no evidence of rust or corrosion could befound. This composition has been applied to a number of cars. Thecoating has good surface characteristics and the cars have been operatedon the road for several months without adversely affecting the coatingand the corrosion protection it affords.

EXAMPLE II A number of test samples were prepared by adding in each case10 pounds of the coating composition of Example I to a 35 pound kettle.Various amounts of polybutadiene polymer oil having a viscosity at 30 C.of approximately 220 poises, as measured by Gardner-Holdt vertical tube,were added slowly at room temperature and mixed in. The polymer oil ineach case was cut both with an equivalent weight of the alkylate ofisobutane and propylene of the coating composition before addition toinsure a more uniform dispersion. Various amounts of cobalt naphthenateas a 6% concentrate in kerosene were then added and the total chargemixed for at least onehalf hour.

The final products were applied to 5" x 10" black iron panels with anairless spray gun. Day to day observations of the panels were made todetermine the time required for a hard, non-tacky film to develop. Thiswas determined by placing the panel on an incline of 15 and rolling agram steel ball and a 10 gram steel ball down the panel. Throughexperimentation it was found that when the balls rolled across thecoated panel under their own momentum with no pickup of theundercoating, the film was satisfactory and it was given a No. 1 rating.If the balls rolled over the film but had some pickup, the film wasrated No. 2. If the balls would not roll down or if they picked up allof the undercoating, the film was rated No. 3. The undercoating filmsalways developed No. 2 and No. 1 ratings with the 60 gram ball beforethe 10 gram ball. This is due to the fact that the undercoating remainstacky for a short period of time after it is able to support the 60 gramball. The momentum of the 60 gram ball is great enough so that thetackiness will not stop it. However, the film is considered satisfactorywhen it can be rated No. 1 with respect to the 60 gram ball since inundercoating applications, road dust will help to do away with thetackiness. The days required for the film to be rated No. 1 with respectto the 60 gram and 10 gram balls were noted.

For comparison the coating compositions without polybutadiene polymeroil and cobalt naphthenate and with polybutadiene polymer oil alone weresimilarly tested.

All of the preparations were also stored in 10 pound pails and examinedperiodically to determine any tendencies toward unusual hardening instorage because of the incorporation of the additives. The results aresummarized in Table I below:

TABLE I Sample Number Composition, Wt. percent:

Coating composition of Ex. I 98. 9 99. 7 97. 8 98. 6 99. 4 97. 4 98. 299. 0 Polybutadiene oil 1. 0 0. 2 1. 8 1. 0 0. 2 1. 8 1. 0 0. 2 Cobaltnaphthenate (6%)- 0. 1 0. 1 0. 4 0. 4 0.4 0.8 0.8 0. 8

Total 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 100. 0 PanelCoverage 1 Days to Number 1 film With 60 gram ball 57 38 32 32 18 15 1413 18 18 13 16 18 With 10 gram ball 62 35 35 23 18 22 18 22 25 20 22 25Storage stability 5 1 Light, metal visible through coverage: Normal,metal not visible through coverage. Sixty gram ball does not leave adeep indenture when it rolls through the film on the first day; Heavy,metal not visible through coverage. Sixty gram ball leaves a deepindenture when it rolls through the film on the first day.

2 Normal.

3 Light.

4 Number 1 filmwhen panel is placed at a 15 angle the ball will rollacross the film with no pickup of product. N 0 longer tacky.

5 Too tacky to pass after 90 days.

f geldency of the product to film over on top in storage.

8 oKvo days. Film forming days. 10 116" film 70 days.

The date of Table I demonstrate the significant reduction in timerequired for formation of a No. l film obtained by use of thecombination of polybutadiene oil and cobalt naphthenate.

In the storage test, Samples 6027, 6025 and 6024 devel- 20 to 40 weightpercent of a mineral lubricating oil, about 10 to 15 weight percent of aparaffinic petroleum resin having a viscosity of about 3000 to 3600 SUSat 210 F. and a viscosity index above about 90, said resin andlubricating oil when mixed having a viscosity of about 200 oped asurface skin after 70 days in storage. However, SUS at 100 F. to 1000SUS at 210 F., about 12 to 16 Sample 6021 containing the highestconcentrations of both weight percent of a water-stabilized calcium soapof fatty butadiene polymer oil and cobalt naphthenate had not acidshaving 12 to 22 carbon atoms, about 3 to 8 weight started to skin overafter 70 days. Although it would appercent of a lead soap of an oxidizedpetroleum wax, and pear logical to expect greater storage surfacehardening 10 about 25 to 40 weight percent of a petroleum solventboiltendency with the samples containing higher additive coning in thenaphtha to kerosene range, said composition tents, this trend is notestablished by the data. A possible having an ASTM worked penetration at77 F. of about explanation for the above observations may be that some290 to 340. samples were subjected to more air exposure before stor- 4.The composition of claim 3 in which said resin and age. Also the amountof material in the storage container said lubricating oil when mixedhave a viscosity of about could affect the results. No significantsurface hardening 400 SUS t 100 F, t 4.00 SUS t 210 F, 111 f g shoflld1" at low Cobalt naphthenate colleen 5. A coating composition consistingessentially of about P partlcularly If 1 Product Contalner 15 Sealed 25to 70% of a mineral oil base consisting essentially of lm'medlatelyafter Packagmg' a petroleum resin having a SUS viscosity at 210 F. ofEXAMPLE III about 500 to 20,000 said resin being at least about 5% of Anumber of samples identified in Table 11 below and Sand F Q P andSin-fluent Funeral lubn catmg 011 to prepared as in Example II weresubjected to the tests provide sa1d ml neral 011 base with a VlOSCOSIlIYof about described in Example II. The polybutadiene oil employed 200 SUSat 100 to 1000' at 210 a about 10 to in these samples containedapproximately 20% styrene of a Water-Insoluble alkallne metal p of afatty and had a, viscosity at C, of approximatgly 1050 8.0101 Of8.1301111 12 110 22 carbon atoms, about 1 '[O 15% Of a poises. Theresults are summarized in Table II. lead soap of oxidized petroleum wax,about 0.1 to 2% of a TABLE 11 Sample Number Composition, Wt. Percent:

Coating composition orEx. I 100.0 99.8 99.1 98.2 98.1 98.9 99.7 97.898.6 99 .4 97 .4 98.2 99.0 Polybutadiene oil 1 0.2 0.9 1.8 1.8 1.0 0.21.8 1.0 0.2 1.8 1.0 0.2 Cobalt naphthenate (6%) .4 0.4 0.4 0.8 0.8 0.8

Tot l 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100.0 100,0100,0 Panel Coverage Days to Number 1 Film: 3

With 60 gram ball 57 50 30 25 15 20 15 16 20 15 19 20 With 10 gramball... (0 33 32 19 27 1s 19 26 18 21 25 Storage stability 9 (1) 1Containing approx. 20% styrene. 5 Too tacky to pass after 90 days.

2 Light, metal visible through coverage; Normal, metal not visible 7 Toosoft and tacky to pass after days. through coverage. Sixty gram balldoes not leave a deep indenture when 8 Too tacky to pass after 40 days.itrolls through the film on the first day; Heavy. metal not visiblethrough 1 Tendency of the product to film over on top in storage.coverage. Sixty gram ball leaves a. deep indenture when it rolls throughOK. the film on the first day. 11 OK 54 days. 3 Number 1 filmwhen panelis placed at a 15 angle the ball will roll 12 OK 30 days. across thefilm with no pickup of product. No longer tacky. OK 40 days. 4 Normal.14 OK 42 days. 5 Heavy. 15 Film forming 42 days.

The data of Table II like that of Table I demonstrate mineraloil-compatible polymer of butadiene and having the advantageoushardening rate obtained when employa kinematic viscosity at 30 C. ofabout 100 to 2000 ing the combination of polybutadiene oil and cobaltnaphpoises, about .003 to .06 weight percent of a naphthenate thenate.of a heavy metal having an atomic number of 2 0 to 82 It is claimed: andsufiicient light hydrocarbon solvent boiling in the 1. A coatingcomposition consisting essentially of about naphtha to kerosene range toprovide a composition hav- 25 to 70% of a mineral oil base consistingessentially of a ing an ASTM worked penetration at 77 F. of about 250petroleum resin having an SUS viscosity at 210 F. of to 350. about 500to 20,000, said resin being at least about 5% 6. The coating compositionof claim 5 wherein the comof said composition, and sufiicient minerallubricating oil position contains about 5 to 20% of said petroleumresin, to provide said mineral oil base with a viscosity of about about20 to 50% of said mineral lubricating oil and about 200 SUS at 100 F. to1000 SUS at 210 F., about 10 to 15 to 50% of said hydrocarbon solvent.

20% of a water-insoluble alkaline metal soap of a fatty 7. Thecomposition of claim 6 wherein the heavy metal acid of about 12 to 22carbon atoms, about 1 to 15% of a naphthenate is cobalt naphthenate.

lead soap of oxidized petroleum wax and sufficient light 8. A coatingcomposition consisting essentially of about hydrocarbon solvent boilingin the naphtha to kerosene 20 to 40 weight percent of a minerallubricating oil, about range to provide a composition having an ASTMworked 10 to 15 weight percent of a paraifinic petroleum resinpenetration at 77 F. of about 250 to 350. having a viscosity of about3000 to 3600 SUS at 210 F.

2. The composition of claim 1 wherein the composition and a viscosityindex above about 90, said resin and lucontains about 5 to 20% of saidpetroleum resin, about bricating oil when mixed having a viscosity ofabout 200 20 to 50% of said mineral lubricating oil and about 15 to SUSat 100 F. to 1000 SUS at 210 F., about 12 to 16 50% of said hydrocarbonsolvent. weight percent of a water-insoluble calcium soap of a fatty 3.A coating composition consisting essentially of about acid of about 12to 22 carbon atoms, about 3 to 8 weight percent of a lead soap of anoxidized petroleum wax, about 0.4 to 1.8% of a mineral oil-compatiblepolymer of butadiene containing up to about 25% styrene and having akinematic viscosity at 30 C. of about 200 to 1200 poises and about .004to 0.02 weight percent cobalt naphthenate and sufiicient lighthydrocarbon solvent boiling in the naphtha to kerosene range to providea composition having an ASTM worked penetration at 77 F. of about 290 to340.

9. The composition of claim 8 wherein said resin and said lubricatingoil when mixed have a viscosity of about 400 SUS at 100 F. to 400 SUS at210 F.

References Cited UNITED STATES PATENTS 2,421,672 6/1947 Wilson et a1.10614 2,815,296 12/1957 Young et a1 1 06-285 X 12 2,816,842 12/1957Westlund et a1. 106-14 2,843,548 7/1958 Westlund et a1. 106-14 FOREIGNPATENTS 667,042 2/ 1952 Great Britain.

OTHER REFERENCES Condensed Chemical Dictionary, 6th ed., ReinholdPublishing Company, New York; pp. 755 and 871. QD 5 C5 (1961) C. 34.

JULIUS FROME, Primary Examiner J. E. EVANS, Assistant Examiner

